Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters

Abstract

Supported gold nanoparticles have excited much interest owing to their unusual and somewhat unexpected catalytic properties1,2,3,4,5,6,7, but the origin of the catalytic activity is still not fully understood. Experimental work4 on gold particles supported on a titanium dioxide (110) single-crystal surface has established a striking size threshold effect associated with a metal-to-insulator transition, with gold particles catalytically active only if their diameters fall below 3.5 nm. However, the remarkable catalytic behaviour might also in part arise from strong electronic interaction between the gold and the titanium dioxide support2,3,5. In the case of industrially important selective oxidation reactions, explanation of the effectiveness of gold nanoparticle catalysts is complicated by the need for additives to drive the reaction5,7,8, and/or the presence of strong support interactions and incomplete understanding of their possible catalytic role1,2,3,5. Here we show that very small gold entities (1.4 nm) derived from 55-atom gold clusters and supported on inert materials are efficient and robust catalysts for the selective oxidation of styrene by dioxygen. We find a sharp size threshold in catalytic activity, in that particles with diameters of 2 nm and above are completely inactive. Our observations suggest that catalytic activity arises from the altered electronic structure intrinsic to small gold nanoparticles, and that the use of 55-atom gold clusters may prove a viable route to the synthesis of robust gold catalysts suited to practical application.

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Figure 1: High-resolution TEM images overlaid with corresponding particle size distributions for unsupported and supported Au55.
Figure 2: Au 4 f electron region of the X-ray photoelectron spectrum of 0.6-wt% Au 55 /BN (black curve) and the corresponding spectrum of a bulk Au reference (grey curve).

References

  1. 1

    Haruta, M., Kobayashi, T., Sano, H. & Yamada, N. Novel gold catalysts for the oxidation of carbon monoxide at a temperature far below 0°C. Chem. Lett. (Jpn) 16, 405–408 (1987)

    Article  Google Scholar 

  2. 2

    Haruta, M. Size- and support-dependency in the catalysis of gold. Catal. Today 36, 153–166 (1997)

    CAS  Article  Google Scholar 

  3. 3

    Haruta, M. et al. Low-temperature oxidation of CO over gold supported on TiO2, α-Fe2O3, and Co3O4 . J. Catalys. 144, 175–192 (1993)

    CAS  Article  Google Scholar 

  4. 4

    Valden, M., Lai, X. & Goodman, D. W. Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties. Science 281, 1647–1650 (1998)

    ADS  CAS  Article  Google Scholar 

  5. 5

    Hayashi, T., Tanaka, K. & Haruta, M. Selective vapor-phase epoxidation of propylene over Au/TiO2 catalysts in the presence of oxygen and hydrogen. J. Catalys. 178, 566–575 (1998)

    CAS  Article  Google Scholar 

  6. 6

    Haruta, M. Catalysis: Gold rush. Nature 437, 1098–1099 (2005)

    ADS  CAS  Article  Google Scholar 

  7. 7

    Hughes, M. D. et al. Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions. Nature 437, 1132–1135 (2005)

    ADS  CAS  Article  Google Scholar 

  8. 8

    Sault, A. G., Madix, R. J. & Campbell, C. T. Adsorption of oxygen and hydrogen on Au(110)-(1x2). Surf. Sci. 169, 347–356 (1986)

    ADS  CAS  Article  Google Scholar 

  9. 9

    Hutchison, J. E. et al. in Inorganic Syntheses Vol. 34 (ed. Shapley, J. R.) 228–232 (Wiley, 2004)

    Google Scholar 

  10. 10

    Lu, P. et al. Polymer-protected Ni/Pd bimetallic nano-clusters: preparation, characterization and catalysis for hydrogenation of nitrobenzene. J. Phys. Chem. B 103, 9673–9682 (1999)

    CAS  Article  Google Scholar 

  11. 11

    Raja, R. et al. Highly efficient catalysts for the hydrogenation of nitro-substituted aromatics. Chem. Commun. 2026–2028 (2005)

  12. 12

    López-Quintela, M. A. & Rivas, J. Chemical reactions in microemulsions - a powerful method to obtain ultrafine particles. J. Colloid Interface Sci. 158, 446–451 (1993)

    Article  Google Scholar 

  13. 13

    Vaughan, O. P. H. et al. Copper as a selective catalyst for the epoxidation of propene. J. Catalys. 236, 401–404 (2005)

    CAS  Article  Google Scholar 

  14. 14

    Haruta, M. Gold as a novel catalyst in the 21st century: Preparation, working mechanism and applications. Gold Bull. 37, 27–36 (2004)

    CAS  Article  Google Scholar 

  15. 15

    Deng, X. Y. & Friend, C. M. Selective oxidation of styrene on an oxygen-covered Au(111). J. Am. Chem. Soc. 127, 17178–17179 (2005)

    CAS  Article  Google Scholar 

  16. 16

    Lambert, R. M., Williams, F. J., Cropley, R. L. & Palermo, A. Heterogeneous alkene epoxidation: past, present and future. J. Mol. Catalys. A 228, 27–33 (2005)

    CAS  Article  Google Scholar 

  17. 17

    Chimentao, R. J. et al. Sensitivity of styrene oxidation reaction to the catalyst structure of silver nanoparticles. Appl. Surf. Sci. 252, 793–800 (2005)

    ADS  CAS  Article  Google Scholar 

  18. 18

    Williams, F. J., Bird, D. P. C., Palermo, A., Santra, A. K. & Lambert, R. M. Mechanism, selectivity promotion, and new ultraselective pathways in Ag-catalyzed heterogeneous epoxidation. J. Am. Chem. Soc. 126, 8509–8514 (2004)

    CAS  Article  Google Scholar 

  19. 19

    Tang, Q. et al. Co2+-exchanged faujasite zeolites as efficient heterogeneous catalysts for epoxidation of styrene with molecular oxygen. Chem. Commun. 440–441 (2004)

  20. 20

    Sebastian, J., Jinka, K. M. & Jasra, R. V. Effect of alkali and alkaline earth metal ions on the catalytic epoxidation of styrene with molecular oxygen using cobalt (II)-exchanged zeolite X. J. Catalys. 244, 208–218 (2006)

    CAS  Article  Google Scholar 

  21. 21

    Boyen, H. G. et al. Oxidation-resistant gold-55 clusters. Science 297, 1533–1536 (2002)

    ADS  CAS  Article  Google Scholar 

  22. 22

    Ono, L. K., Sudfeld, D. & Cuenya, B. R. In situ gas-phase catalytic properties of TiC-supported size-selected gold nanoparticles synthesized by diblock copolymer encapsulation. Surf. Sci. 600, 5041–5050 (2006)

    ADS  CAS  Article  Google Scholar 

  23. 23

    Takahiro, K. et al. Core level and valence band photoemission spectra of Au clusters embedded in carbon. J. Appl. Phys. 100, 084325 (2006)

    ADS  Article  Google Scholar 

  24. 24

    Wertheim, G. K. & Dicenzo, S. B. Cluster growth and core-electron binding-energies in supported metal clusters. Phys. Rev. B 37, 844–847 (1988)

    ADS  CAS  Article  Google Scholar 

  25. 25

    Santra, A. K. & Goodman, D. W. Oxide-supported metal clusters: models for heterogeneous catalysts. J. Phys. Condens. Matter 15, R31–R62 (2003)

    ADS  CAS  Article  Google Scholar 

  26. 26

    Miller, J. T. et al. The effect of gold particle size on Au–Au bond length and reactivity toward oxygen in supported catalysts. J. Catalys. 240, 222–234 (2006)

    CAS  Article  Google Scholar 

  27. 27

    Bowker, M., Nuhu, A. & Soares, J. High activity supported gold catalysts by incipient wetness impregnation. Catal. Today 122, 245–247 (2007)

    CAS  Article  Google Scholar 

  28. 28

    Haruta, M. Catalysis of gold nanoparticles deposited on metal oxides. CATTECH 6, 102–115 (2002)

    CAS  Article  Google Scholar 

  29. 29

    Briggs, D. & Seah, M. P. (eds) Practical Surface Analysis 2nd edn (Wiley, 1990)

    Google Scholar 

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Acknowledgements

M.T. and O.P.H.V. acknowledge financial support from the UK Engineering and Physical Sciences Research Council and King’s College, Cambridge, respectively.

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Correspondence to Richard M. Lambert.

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Supplementary Figures

This file contains Supplementary Figures 1 and 2 with Legends that describe the characterization of the 0.6 wt% Au/SiO2 catalyst prepared using PVP method and the characterization of the 1 wt% Au/C catalyst prepared using the microemulsion method, respectively; Supplementary Table 1 giving a full statistical breakdown of the particle size distributions of all catalysts; Supplementary Figures 3 and 4 with Legends and Supplementary Discussion describing the effect of catalyst thermal treatment; and additional references. (PDF 1878 kb)

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Turner, M., Golovko, V., Vaughan, O. et al. Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters. Nature 454, 981–983 (2008). https://doi.org/10.1038/nature07194

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